Si-H Bond Activation of Alkynylsilanes by Group 4 Metallocene Complexes

0342073 - ÚFCH JH 2011 RIV US eng J - Journal Article
Lamač, Martin - Spannenberg, A. - Baumann, W. - Jiao, H. - Fischer, Ch. - Hansen, S. - Arndt, P. - Rosenthal, U.
Si-H Bond Activation of Alkynylsilanes by Group 4 Metallocene Complexes.
Journal of the American Chemical Society. Roč. 132, č. 12 (2010), s. 4369-4380. ISSN 0002-7863. E-ISSN 1520-5126
Institutional research plan: CEZ:AV0Z40400503
Keywords : Si-H bond activation * alkynylsilanes * metallocene complexes
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 9.019, year: 2010

The reactivity of variously substituted alkynylsilanes toward selected group 4 metallocene complexes was investigated. Reactions of the alkynylsilanes (RC2SiR2H)-C-1-H-2 (R-1 = SiMe3, R-2 = Me, 1; R-1 = SiMe3, R-2 = Ph, 2; R-1 = SiMe2H, R-2 = Me, 5) with Cp2TiMe2 (Cp = eta(5)-cyclopentadienyl) resulted, upon methyl group transfer to the silyl group, in the previously described titanocene alkyne complexes Cp2Ti((RC2SiR2R3)-C-1-R-2) (R-1 = Me3Si R-2 = R-3 = Me, 3; R-1 = HMe2Si, R-2 = R-3 = Me, 6) or the unreported complex 4 (R-1 = Me3Si, R-2 = Ph, R-3 = Me). The Cp2TiCl2/n-BuLi system yielded alkyne complexes 6 and 7 (R-1 = HMe2Si, R-2 = Me, R-3 = H); no alkyl group transfer was detected. On the other hand, reactions utilizing the Cp2ZrCl2/n-BuLi system afforded inseparable mixtures; however, complexes of the type Cp2Zr[(RC2SiMe2)-C-1(n-Bu)] (R-1 = Me3Si, 8; R-1 = HMe2Si, 9) were detected.
Permanent Link: http://hdl.handle.net/11104/0184901